DE1495538A1 - Soluble diphenyl ether polymers and process for their preparation - Google Patents

Description

The present invention relates to new soluble polymers, which contain a variety of diphenyl ether groups. In particular, the invention relates to soluble polymers in which the Polymer matrix in large quantities a variety of di » contains phenyl ether residues bound with methylene bonds are. The invention very particularly relates to soluble diphenyl ether homopolymers and derivatives thereof, as well as a process for their manufacture.

In recent years, the immense extent of the usability for soluble polymers has led to an eager search led to new materials. Ghana are particularly welcome water-soluble polymers. For example, water

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soluble synthetic polymers for such different applications ”such as adhesives“ detergents ”drilling mud additives. Flocculants and thickeners for food products »enfowiok ^ to The characteristics of these polymers, including solubility», are clearly related to their structure and their composition. Soluble polymers must not have excessive crosslinking between neighboring polymer chains, since such bonds quickly destroy solubility.

It has been known for some time that chloromethyl diphenyl ether and other similarly reactive diphenyl ether derivatives easily Condensation polymerization to an insoluble, crosslinked, resinous product. This polymerization comprises the condensation between a reactive halomethyl group of a halo-diethyldiphenyl ether molecule with a © i * second diphenyl ether group with formation of a methylene chain and simultaneous elimination of hydrogen halide. the The basic reaction in this condensation is explained in equation 1 »where X means chlorine or bromine!

XGH ₂ - (01.1)

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Ee can be seen that both networking and further Polymerization through the continued reaction of the remaining Halomethyl groups take place with other diphenyl ether radicals can. Since the reaction is unfeep, formation of cross-linking methylene bridges is the same as it occurs when the polymer chain is lengthened «is the final condensation polymer practically almost always a highly cross-linked resin-like poly * merisat that works in most polar and non-polar solvents is insoluble. Only if there is a deficiency in halomethyl groups or is present at reactive sites «soluble polymers are obtained» because of the thermal stability of the Diphenyl ether and the possibilities «different functional groups through chemical reaction with the rest introducing reactive groups «would be a soluble condensation» · »polymer« which contains a large number of diphenyl ether groups « highly desirable. A soluble diphenyl ether homopolymer would be particularly advantageous with the remaining halomethyl groups contains.

It has now been found that soluble diphenyl ether polymers / which a multitude of diphenyl ether residues «associated with. Methylene bond " contain «can be obtained by condensation polymerization of a reactive aromatic material« the following® contains P-components i

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1. A larger proportion by weight of a diphenyl ether the general formula

(D

in which the radicals A, which can be the same or different » Represent hydrogen atoms or the group -CHLY »where Y has the meaning Cl, Br, OH or OR» and R is an alkyl group represents having 1 to 4 carbon atoms and

2. on average about 1.0 to 3.5 groups -CH _g Y per molecule ι

this polymerization is carried out in the presence of a suitable, non-reactive diluent and a Friedel-Crafts catalyst at a temperature in the range from about 0 to 85 ^° C. The soluble diphenyl ether condensate polymer obtained contains a relatively large proportion of a large number of radicals of the general formula

(II)

wherein each substituent A has the meaning given above;

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The polymer is "as expressed by its solubility in such non-polar organic solvents" as for example 1,2-dichloroethane and toluene at concentrations of 1 to 10 wt .- ^ or more "free of any substantial crosslinking and is essentially linear and weakly branched polymer chains. It is a light colored, stable solid substance * which can be isolated from the reaction mixture by precipitation with a polar diluent such as methanol, by evaporation of the diluent or by other customary measures. After purification by reprecipitation from a suitable mixture of solvents such as dioxane and methanol, it is practically colorless. A 10% strength by weight solution of polymer in 1,2-bichloroethane has an Ostwald viscosity of about 1.3 to 25 μP at 25 ^e 0.

It was also found that by condensation in the presence a suitable diluent prepared soluble Diphenylätherpolymerlsate as intermediates in the synthesis of new and valuable soluble cationic polymers can be used. For example, through implementation residual halomethyl groups in the soluble polymer with a suitable tertiary amine or an organic Sulphide quaternary ammonium or sulphoniam groups are chemically bound to the polymer matrix. By introduction a suitable number of hydrophilic cationic substituents,

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generally at least 0.3 cationic. Groups per diphenyl ether residue, very valuable water-soluble products are obtained.

These cationic polymers and especially the quaternary ones Ammonium and sulfonium derivatives have properties which they do making it exceptionally valuable for a variety of uses. For example, water-insoluble products are particularly valuable = fully in a solvent extraction process to remove Anions from aqueous solution. See water-soluble products of their own as flocculants, thickeners and binders. Since the Diphenyl ether polymer matrix exceptionally resistant to thermal and oxidative attack is »these materials have an unusual chemical and thermal stability, moreover points the manufacture of these materials because of such factors as, for example, relatively cheap raw materials, the Stability of the soluble intermediate polymer and the ease with which the desired substituents are attached to the polymer matrix can be bound, significant. and distinct procedural advantages and economic advantages.

The term "soluble" as used here and in the general description is used means in a liquid solvent to form a visually homogeneous and practically transparent solution distributable, which can be infinitely diluted with the same solvent «When characterizing the solubility

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of the polymer were methylene chloride, 1,2-dichloroethane, Toluene and heptane are used as typical non-polar organic solvents while water and aqueous alcohol are polar Represent solvents. In accordance with the usual In practice, the term "halomethyl" "as used herein" includes both chloromethyl and bromomethyl groups.

In order to understand the invention, it should be pointed out “that Diphenyl ether is to be understood as a reactive aromatic compound, which is preferred in electrophilic substitution reactions at the o- and p-positions to the ether oxygen enters. In In practice, only four positions are generally accessible, since after substitution of one o-position of each ring the reaction occurs is sterically hindered in the other o-position. For example, the chloromethylation of diphenyl ether gives a mixture of chloromethyl diphenyl ethers which contain 1 to 4 chloromethyl groups per di-phenyl ether residue. The exact composition depends on the reaction conditions and especially on the amount of chloromethylating agent used. Several typical Chloromethyldlphenyl ether (CMDPX) compositions are given in Table I.

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Table I.

Typical chloromethyl diphenyl ether compositions

CMDPÄ

17 25 32 33

g wt # Cl 17.6 25.2 32.0 33.6

S molar ratio 8 CICH ^ / DPÄ 1.12 1.85 2.80 3.0

^ Composition (Mol-Jfe):. »

^ Diphenyl ether (DPK) 17.3 0

n> 2-chloromethyl-DPK. 5.3 0.3

4-chloro-ethyl-DPK 42.9 2.4

2,4 "-Bis (chloromethyl) -DPK 10.8 17.7

4,4'-bis (chloromethyl) -DPK 20.6 68.5

Tris (chloromethyl) DPK 2.3 10.5

Tetrakis (chloromethyl) DPK <1 < 1

(a) 17 % 2,2 ', 4- and 72 % 2,4,4 "-Tris- (chloromethyl) -DPK' * -

cn cn co 00

0, 0 0 0 0 0 1.9 1 8.6 16.5 89 ^(a) 66.5 <2 16.5

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It is often advantageous to use a crude mixture of halomethyl diphenyl ethers with an average of about 1.0 to 3.3 halomethyl groups per diphenyl ether residue, such as the crude chloromethylation products shown in Table I, as the reactive aromatic material in the modified condensate polymerization process described here . However, pure mono- * bis- or trish & logenmethyldiphenyl ethers can also be used. In addition, minor amounts of up to 10 or 20 wt -. Reactive% of other, nichthalogenraethyl-aromatic materials such as diphenyl ether or a soluble polystyrene present in the reaction mixture "provided that on average at least about 1.0 halomethyl groups per molecule reactive aromatic material are present ₀ At least some of such other reactive materials are chemically bound in the polymer matrix.

In the polymerization of various chloromethyl diphenyl ethers, such as the crude mixtures shown in Table I using the polymerization procedure described herein was found to be an average of about 1 * 0 Chloromethyl groups per biphenyl ether residue in the condensation reaction is consumed. For example, a crude chloromethyl diphenyl ether with a content of 31 * 5 Qew. ~ # In side chain bound chloride and an average of 2.65 Chlomethyl groups per Diphenylätherrest in 1,2-Diohloräthan under

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Formation of a soluble polymer polymerizes which contained 22.1% by weight of residual chlorine or an average of about 1.60 chloromethyl groups per diphenyl ether residue. Similar results are obtained with other diphenyl ether monomers. In fact, theoretically only one halomethyl group per monomer unit should be consumed in the formation of a high molecular weight linear condensation product.

An initial halomethyl content greater than about 3 * 5 is generally undesirable, especially with a! Homopolymer! - sation, since reactive sites must also be present on the aromatic nuclei for the formation of the necessary methylene bridges. More halogen-methylated diphenyl ethers can be mixed with other reactive, non-halomethyl aromatic materials can be used provided that the average halomethyl content of the monomer mixture is in the range of about 1.0 to 3.5 Halomethyl groups per molecule.

Halomethyl groups that are in excess over those from the polymerization used number are present, remain as a substituent on the polymer matrix and result in the possibility of further chemical reactions. The number of remaining halomethyl groups depends of course on the initial halomethyl content of the monomer. In the homopolymerization of chlorine thyldiphenyl ether were soluble products with a content of only

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1 to 25 or more parts by weight of chlorine bound in the side chain or an average of about 0.05 to 2.0 or more residual chloromethyl groups per diphenyl ether residue. So can by suitable choice of the initial monomer, soluble diphenyl ether polymers of largely different compositions obtain.

It is true that the well-known halomethylation of diphenyl ether is one preferred method for obtaining the reactive Diphenyläthermonc -meren for use in the inventive method, but the side chain chlorination or bromination of a suitably alkyl-substituted diphenyl ether, such as, for example, ditolyl ether, constitutes an alternative route for the synthesis of the monomers. Other Diphenyläthermonoraere, which in solution with the formation of the desired polymer matrix of diphenyl ether groups that are linked with methylene bonds can be polymerized * apparent to those skilled in the art. For example, the solution polymerization of an alkoxymethyl or hydroxylmethyldiphenyl ether with an average of about 1.0 or more alkoxymethyl or hydroxymethyl groups per molecule a similar soluble Diphenylätherkondensaticnspolymerisat.

In the solution or suspension polymerization according to the invention process is the type of solvent or diluent used liquid particularly critical. It can be seen

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that such a liquid should be practically inert under the usual polymerization conditions. For the sake of convenience in carrying out, including extraction of the polymer and the diluent "is a liquid preferably with a Normalsledepunkt ranging from about] 50 ^o C to 150 C ^e.

'It has been found that halogenated aliphatic hydrocarbons » substances with 1 to 4 carbon atoms, such as carbon tetrachloride, methylene chloride, ethylene dichloride, ethylene triohloride, Bromohloräthan, Hethylendlbromid and propylene dichloride are particularly effective in achieving a homogeneous polymerization mixture. These solvents are generally preferred. Liquid saturated aliphatic hydrocarbons such as for example, heptane and cyclohexanes are also suitable if they are subjected to vigorous agitation to achieve a fine Dispersion or suspension of the reagents can be used. Halogenated aromatic liquids such as chlorine or o-dichlorobenzene can be used. Aromatic hydrocarbons such as toluene are benzene or xylene, good solvents for the reactants, however some, especially toluene, are sufficiently reactive as monomers to take part in the polymerization reaction, which is both the remaining halomethyl content and the chain length of the Polymer product. Contains oxygen © Solvent ^

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such as dioxane, acetone, alcohols and glycol ethers unsatisfactory »since they are polymerizing, probably prevent by inactivating the catalyst * »

Typical Friedel-Crafts catalysts are used in the present case Solution or dispersion polymerization processes are used are aluminum chloride «stannous chloride, stannous chloride, zinc chloride» Ferrous chloride and sulfuric acid. Generally will the milder catalysts, and in particular tin carbon and stannous chloride, are preferred because they are more selective in the desired linear Polymerization without crosslinking by the remaining halomethyl groups favor. Aluminum chloride is an effective one Catalyst, however, it is less soluble in the preferred chlorinated aliphatic Kohl @ nwa @ sex> stoffv @ rdilnnungsmltt @ ln. Since the polymer has a tendency to crosslink on the surface © of the undissolved catalyst particles was observed, catalysts are advantageous which are at the desired concentration are completely soluble. Generally a catalyst concentrate in the range from about 0.1 to 1 * 0 wt .- ^ or more, based on the content of reactive aromatic monomer, satisfactory.

In the practical implementation of the method according to the invention wix ° d a'homogeneous Folymerisationssy ^ te ^ with a halogenated aliphatic hydrocarbon solvent and zinc chloride

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or stannous chloride is preferred as the catalyst. The exact amount solvent is generally not critical. However, at a solvent to monomer weight ratio of less than 0.5 difficult «to obtain the desired degree of polymerization without gel formation. Usually a solvent / Monomer ratio of about 1 to 5 is preferred. At a solvent / monomer ratio greater than about 10, a higher catalyst concentration may be required to achieve a suitable one To achieve Polymerisationsgesehwindigieeit.

To carry out the polymerization, the reaction mixture containing the monomer »catalyst and diluent» is ^{heated with agitation at a temperature in the range from 0 to 85 °} C. for sufficient time to achieve the desired polymerization. Although the rate of reaction depends on such other factors as, for example, the concentration of monomer or catalyst, the rate of reaction at a temperature below about 0 ° C. is generally too slow for practical purposes. At temperatures above 85 ^° C., it is difficult to prevent noticeable crosslinking, even when diluted considerably with solvent. In practice, it is generally expedient to work at a temperature in the range from 20 h ± & 85 ^° C. and preferably in the range from about 40 to 70 ^° C.

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To achieve the desired degree of polymerization, a Response time of 0.25 to 20 or more hours may be required. The extent of the reaction can be determined by observing the viscosity of the reaction mixture, determined by analyzing samples of the product for halogen content or by other customary methods will. The viscosity of the product is a particularly important control factor. Usually there is a gradual increase in Observe solution viscosity as polymerization progresses. Then there is a sharp increase in the viscosity of the solution, usually just before the product gels. About education To prevent any substantial amounts of insoluble crosslinked polymer, the reaction will be carried out before or upon observation this sharp increase in viscosity is terminated by adding sufficient water, alcohol or another material to inactivate the catalyst.

The polymerization is usually carried out at atmospheric pressure with appropriate provision being made for venting or removing the hydrogen halide formed as a by-product. Sometimes a slightly reduced pressure can be of the order of magnitude of a more rapid removal of the hydrogen halide to reach. Alternatively, ssur maintaining a liquid phase with a low-boiling solvent can be a massive one Pressure to be applied.

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Loose cationic diphenyl ether polymers

In addition to the above-described soluble Dlphenylätherpolymerlsat @ n and the method for their manufacture, it was further found that cationic groups (Z) chemically to the matrix of the soluble diphenyl ether, conversion of the remaining »to the polymer bound halomethyl groups with suitable reagents, such as for example organic amines or sulfides can. The cationic groups are therefore attached to the polymer as substituents of the general formula

-CH ₂ Z bound.

The introduction of an average of more than about 0.3 hydrophilic cationic groups per diphenyl ether residue usually results in a water-soluble product, especially when the cationic groups A quaternary ammonium or group made with a water-soluble amine or sulfide of low molecular weight Is sulfonium group. At less than average about 0.2 hydrophilic cationic groups per diphenyl ether residue results in Product usually a cloudy or opaque mixture with water. Some of these weakly substituted cationic derivatives are Soluble in alcohol, but with an average of less a!, s The products are about 0.1 cationic groups per diphenyl ether residue

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soluble only in non-polar organic solvents.

It is through a suitable choice of the reaction components and, in particular, of the halomethyl content of the diphenyl ether polymer possible »new and valuable soluble cationic © products with a wide range of solubility and capacity Maintaining functionality «The water-soluble cationic diphenyl ether polymers are effective as flocculants in aqueous systems «while the water-insoluble cationic ones Derivatives are valuable as extractants for removing anionic from aqueous process streams.

Soluble "strongly basic" quaternaries are particularly desirable Ammonium derivatives «by reaction of a soluble diphenyl ether polymer can be obtained with a tertiary amine. For a water-soluble product, the polymer used as an intermediate should have at least 0.3 residual halomethyl groups each have diphenyl ether residue and for a product with high capacity is the use of a polymer with a high residual halogen methyl content more advantageous as an intermediate product, for example the product of the homopolymerization of a chloromethyl alcohol ßiphenylathers with a content of 30 or more Oew * - $ chlorine.

The desired qw? T @ x <nary ammonium derivatives can be easily using in high yields under mild conditions

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tertiary amines of the general formula

R ₁

/ ^l N - R ₂

produce * in which the groups R represent hydrocarbon radicals, which have no substituents other than hydroxyl groups. The hydrocarbon radicals can in each case be aliphatic and aromatic or alicyclic groups, or with one another part of a 5- or 6-membered heterocyclic ring which forms the tertiary Contains nitrogen atom.

The amination can also be carried out with ammonia and with primary and secondary amines including alkylenepolyaraines, i.e. with Amines of the above formula in which at least one of the groups R represents a hydrogen atom, with the formation of other valuable * soluble cationic derivatives.

In particular, new and valuable cationic derivatives of a soluble diphenyl ether polymer with residual halomethyl groups be obtained mits

(1) Amines of the general formula

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wherein Rj * R ₂ and R, each hydrogen atoms «G ₁ -G ₁ Q cycloalkyl, aryl or aralky! hydrocarbon groups, C ₁ -C ^ - monohydroxyalkyl groups or Cg-C ^ dihydroxyalkyl groups, provided that the amine does not contains more than one aromatic radical;

(2) Alkylene polyamines of the general formula

where a is an integer from 2 to 6 and b is an integer represent an integer from 1 to 4;

(3) monocyclic amines consisting of a 5- or 6-membered ring consist of 1 to 2 heterocyclic? Contains nitrogen atoms, or 0, -Cj, -alkyl derivatives thereof and

(4) heterocyclic polyamines, namely hexamethylenetetramine or Trialkyloyelotrimethylontriamines with 1 to 4 carbon atoms,

Typical of the tertiary amines, which are particularly two-fold The following are valuable cationic derivatives, such as trimethylamine, tri-n-butylamine, dimethylaminoethanol, dimethylisopropanolamine, dimethylbenzylamine, dimethylaniline, dimethylcyclohexylamine, N, N-dimethylamino-1, 2-propanediol, methyldiethanolamine and dimethyldodetoylamine as well as such

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tertiary heterocyclic amines "such as pyridine, N-Methylraorpholin, pyrrole" N-ethylpiperidine, hexamethylenetetramine, and Trialkyltrimethylentriamine, were obtained by condensation of Poroaldehyd and a primary aliphatic amine having 1 to 4 carbons "· s to ff atoms <Typical of these A large number of primary and secondary amines which can be used are: methylamine, diisopropylamine, methylethanolamine, N-methyl aniline, piperidine, 2,5-dimethylpiperazine, 2-aminoethanol, isopropanolamine and such alkyl polyamines as ethyleneline, propylenediamine, 1, 6-Dlaminohexane and Diethylenetriamine.

In practice it is often useful to use an aqueous solution of the desired amine to use. Mixtures of 2 or more amines can also be used. With polybasic amines, in particular In the case of an alkylene polyamine, care must be taken to prevent excessive crosslinking. However, using a substantial excess of the alkylene polyamine became valuable soluble derivatives produced.

The amination of the soluble halogenomethyldiphenyl ether polymer used as an intermediate is generally easy at a temperature between about 0 and 60 ° C. A temperature between about 20 and 45 ° C is often preferred. It can Amination in the absence of a solvent by carefully mixing the polymer intermediate and an anhydrous amine

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be achieved «however, the process is preferably carried out in the presence of a liquid solvent in which both the AmIn as well as the polymer intermediate is soluble * like for example toluene * methylene chloride or ethylene dichloride. The solvent used as a diluent in the polymerization can often be used in the amination eliminates the need to isolate the polymer intermediate. In many cases it is both effective and two-way to add the polymerization mixture after the desired one Degree of polymerization is reached, add an aqueous solution containing an excess of the desired amine. Am 10 to A large excess of amine, based on the remaining halomethyl content of the polymer intermediate product, is often sufficient. That The mixture is then stirred at the desired temperature until the amination has ended. A response time in the range of A few minutes to several hours is generally sufficient, but a longer time may be required for less active amines.

If an aqueous solution of AmIn is used, that will cationic amination product usually obtained in the aqueous phase. For many purposes it can be satisfactory without Isolation from the solution can be used. However, if necessary, the product can be removed by evaporating the solvent or be isolated by other customary methods.

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Still other cationic derivatives can be obtained by reacting the soluble halomethyldlphenyl used as an intermediate » ether polymer made with an organic sulfide will. The sulfonium derivatives obtained from sulfides of the general formula are particularly desirable

SR ₄ B ₅

are prepared wherein R ₄ and R ₁ . each have the following meaning (l) C 1 -C 6 -alkyl groups * (2) C ₂ -C ₂ -monohydroacyalkyl groups, (3) Cj-Cg-haloalkyl groups, (4) C "-C ₁₂ -aralkyl groups and (5) the Group "" Gj _n HgJm ⁰⁰⁰ ^ * ^{where ra is an} integer from 1 to and Q is a hydrogen atom, an alkali metal cation or an alkyl group having 1 to 6 carbon atoms. Typical organic sulfides that can be used are dimethyl sulfide, n-butyl methyl sulfide, 2- (Methy] jner-capto) -ethanol, bis- (2-hydroxyethyl) -sulfide and methyl-3-methylthiopropionate. Generally the use of one is organic sulfids are preferred in which one of the substituent groups does not contain more than 2 carbon atoms.

It is true that the reaction of the halomethyldiphenyl ether polymer used as an intermediate takes place with an organic one Sulphide is not as rapid as amination, but can be done under similar conditions using an appropriate diluent and a reaction temperature between 20

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and 60 * C. Often a response time of Takes 2 to 20 hours or more for full conversion * With a low boiling solvent or reactant it may be necessary «to apply moderately increased pressure.

Another type of cationic derivative is obtained by reacting the soluble halomethyldiphenyl ether polymer used as an intermediate with a tert-dialkylamino-phosphine in a manner known per se to form a quaternary phosphonolum derivative. In addition, it can be seen that "by suitable choice of the reaction components" the Molar ratios and the reaction conditions the production of products is possible «which is more than one type of cationic Groups contain “for example a polymer” which contains both quaternary ammonium and sulfonium groups.

The above cationic derivatives are prepared from a halomethyldiphenyl ether polymer used as an intermediate which is normally a halide counteranion, i.e. chloride or contains bromide. In the worst case, however, a Such halide form can be converted into other forms with reactive anions in a conventional manner by conventional ion exchange procedures such as sulphate «bsulphate» nitrate «carbonate, acetate or citrate can be converted.

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The following examples illustrate the invention "without ei · limit. Unless otherwise stated, all parts and percentages are based on weight.

example 1 Solution polymerization

To a solution of 20,570 parts ohlormethyliertem diphenyl ether having a content of 34.1 wt -.% Chlorine, 19 500 parts of 1,2-Diohloräthan 25.9 parts of anhydrous stannic chloride was added with stirring. The mixture was then ^{heated at about 68 °} C. and its viscosity was observed as hatred of the extent of the polymerization. After 7.25 hours, when the viscosity indicated the gel point was near, 24,000 parts of water were added with thorough mixing to stop the reaction. The mixture was cooled to room temperature and the organic phase was separated. This solution of soluble diphenyl ether polymer in 1,2-dichloroethane was washed a few more times with water and was then ready for any further desired processing.

A sample of the soluble polymer was made from the 1,2-chloroethane solution isolated by precipitation with excess methanol. The light yellow-brown powder substance was dissolved by dissolving Purified in dioxane and reprecipitation with methanol, which gave a practically white product, which according to the analysis

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26.9 wt .- # contained chlorine bound in the side chain. One A sample of the isolated polymer as a 10 # solution in 1,2-dichloroethane had an Ostwald viscosity of 2.52 eP at 25 ° C. The initial chloromethylated diphenyl ether had a viscosity under the same conditions of 1.17 <* P

Example 2 Polymerization conditions

Using the general procedures described in Example 1, a variety of liquid diluents were prepared and polymerization catalysts in the polymerization of chloromethyldiphenyl ether investigated. As evidenced by the development of HCl resulted in an increase in solution viscosity and the formation of a solid, low chlorine product the polymerization in the presence of many diluents and a variety of Friedel-Crafts catalysts. But when Toluene and o-xylene were used as diluents, the sharp decrease in the residual chlorine content indicated that the solvent was reacting with the monomer and / or the polymer would have. When using acetone, dioxane or a diethylene glycol ether as a diluent, there was no noticeable Polymerisation.

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The values of a number of typical trials using of diluents «which are practically inert under normal reaction conditions are given in Tables XI and III.

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Tabel II

Polymerisation sverdttn nwvpt gnii ttcl
(SnCl ^ as a catalyst)

Cl

Verse. Diluents Dilution
medium
ratio (a) Cataly-
sator
konz.fb) T »C Time,
Hours. Monomer polymer viscosity CO
O
to 3A-1 1,2-dihlorethane 1.0 0.2 % 64 0.6 31.5 22.1 6.33 oP 819 3A-2 Carbon tetrachloride
material 1.0 0.6 % 74 1.7 31.5 22.5 4.03 eP 3A-3 Methylene chloride 1.0 0.2 % 20th 1.1 31.5 22.4 - cn
KJ 3A-4 Heptane 0.6 0.2 % 75 2.0 31.5 24.5 2.42 cP 3A-5 isoootan 0.8 0.2 % 68 1.5 33.1 23.0 1.96 cP 3A-6 o-dichlorobenzene 1.3 0.5 % 60 2.7 34.8 24.8 2.15 cP

(a) Diluent / CMDPX weight ratio

(b) Ji by weight based on CMHPX

(o) 10 % in 1,2-DiohlorXthane at 25 ° C

Ver
search catalyst Table III 1,2-dichloro-64
ethane
1,2-dichloro-83
ethane tneen Weight: % Cl Visco
sity 3B-1
3B-2 SnCl ₄ Polymerization catalysts 1,2-dichloro-80-87
ethane Time,
Hours. Monomer polymer 6.33 cP
8.02 cP 3B-3 -_ __ in j
ant * ig HtigO * 1,2-dichloro-3O-5O
ethane 0.6
1.25 31.5
30.2 22.1
21.3 1.88 cP 3E-4 H ₂ SO ₄ Conditional Tetraohlor- 74
I.aUI ****** 4m j *. J * Wed 6th 30.2 19.5 1.30 cP 909819 / 3B-5 AlCl C °) Catalyst diluent
conc. medium (a) T ^e C 16 31.6 19.5 1.44 cP cn
NJ 0.2 %
0.7 % 32 31.6. 24.8 1.3 % 7.0 ^ 3.0 Jf

(a) Dilution ratio: 0.7 to 1.5

(b) Added as a 50% solution in methanol

(c) Only partially solved

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Example 3 CMDPÄ monomers

The general polymerization procedure described in Example 1 was carried out on various (ailomethyldiphenyl ethers including crude chloroethylation products such as them for example shown in Table I, as well as purified compounds. The values from a number of typical Experiments are given in Table IV.

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Table IV CMDPX monomers

(1,2-dichloroethane, 0.2 %

Ver
search Oew.-ji
Cl ClCH ₀ - /
DPA ² Dilution
medium-sized
ratio conditions
Time,
T ^e C hours 2.1 Polymer
3ew.- £ Cl viscosity 8.62 CO
OD 4-1 17.4 1.07 1.0 20-65 1.9 <2 14.55 CO 4-2 22.1 1.51 2.0 40 1.3 8.8 - - * 4-3 26.6 ^(a) 2.00 6.5 35-50 0.6 9.4 6.33 cn 4-4 31.5 2.67 1.0 64 5.5 22.1 2.22 4-5 34.8 3.18 1.3 5-10 23.3

(a) Pure 4,4'-bis (chloromethyl) diphenyl ether

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Example 4

200 parts of a 1,2-diethylethane solution were introduced into an oil reaction vessel, the 134.5 parts of a soluble chloromethyldiphenyl ether polymer with 21.8% residual rare chain chlorine (0.83 mol -CH ₂ Cl) and a viscosity of 1.87 oP contained as a 10-strength solution in 1,2-Dlohloräthan. 195 parts of water containing 2.5 parts of sodium hydroxide and then 386 parts of 25% aqueous trimethylamine (1.6 mol) were introduced into the reaction vessel with stirring. As the amination progressed, the reaction temperature rose to 45 ° C. The temperature was then ^{kept at about 45 °} C. for a further 2 hours in order to ensure complete conversion before the clear, colorless solution was concentrated in vacuo to remove excess trimethylamine and the 1,2-chloroethane. Finally the pH of the viscous aqueous solution of the remaining product was adjusted to 7 + 1. The amination was practically quantitative as determined by analysis of the chloride ion. The Brookfield-Viekosität a 20 £ lgen aqueous solution of Methylentrimethylammoniumderivates of Dlphenylätherpolymerlsates was 17 oP at 23.9 ⁰ C (75 ^e P) and the pH of 7 »0th .

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Example 5 Other ammonium derivatives

IAa to show the broad range of ammonium derivatives that can be derived from the soluble chloromethyldiphenyl ether polymer used as an intermediate product "can be produced * are a number of typical aminations are summarized in Table V. In tan In most cases the two-phase solvent system, w ** eer-1,2-di-chloroethane, is satisfactory. With less water-soluble However, 1,2-dichloroethane can be used alone or mixed with amines aqueous alcohol may be preferred.

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Table V
Other ammonium derivatives

reaction

Ver
search Polymer
Oew.-g
Cl Amine Molver
ratio
Amine / -CH ₂ C1 T * C Time,
hours product ι 7-1 21.8 Tri-n-propylamine 1.5 50 5 water soluble Vd
Vji
"" ν I 7-2 25.5 Tri-n-butylamine 1.5 45 16 water soluble 7-5 21.8 Dimethylaminoethanol 1.5 50 0.5 water soluble CO 7-4 25.5 2-aminoethanol 1.5 25-50 2 water soluble CO 7-5 21.0 Pyridine 1.45 42 6th water soluble OO 7-6 25.5 N, N-dimethylanal 2.2 54 1 water soluble CO 7-7 21.0 Dimethyldodeoylamine 1.2 25i'45 5 alcohol soluble * ^a ' __ »
cn 7-8 21.5 / Hexamethylenetetramine
^ Trimethylamine 0.5
0.7 40 1 water soluble »• ο 7-9 25th / Trimethylamine
iDlmethylamine 0.8
0.45 40-70 0.67 water soluble

(a) Soluble in methanol, isopropanol and 50% aqueous isopropanol

cn cn co oo

Example 6 Alkylene polyamine derivatives ■ '

40 parts of anhydrous ethylenediamine were quickly added to a solution of 5 parts of precipitated chloromethyldiphenyl ether polymer in 10 parts of 1,4-dioxane. The mixture became more noticeable Development of heat of reaction light yellow. After 2 hours at room temperature, the clear solution was diluted with 150 parts of water. The product was completely soluble. The amination was complete, as revealed by the chloride analysis.

A soluble derivative was also prepared in a corresponding manner by using a large excess of diethylenetriamine. These are water-soluble alkylene polyamine derivatives effective flocculants.

Example 7 Sulfonium derivatives

A. The polymer solution described in Example 1 was diluted with about 28,000 parts of 1,2-dichloroethane and dried duröh azeotropic distillation. The clear solution obtained was mixed with 8000 parts Diäthylenglykolather and heated at about 50 ^# C. Then 16,610 parts of thiolodiglycol were slowly added to the mixture over the course of 1 to 2 hours with stirring. "

909819/1152 bad original

while a Binphaeeneystera was maintained. Well another Heating at 50 to 55 ° C for several hours gradually increased to 12,300 Parts of water were again added while maintaining a single-phase system. Finally another 12,500 parts of water were added quickly added and the Ij2-Diohloräthan was stripped off in vacuo to obtain a clear, viscous solution of the bis (2-hydroxyethyl) sulfonium derivative in aqueous glycol ether. That I the sulfonium derivative slowly in the absence of the solvent decomposed «it is preferably stored as an aqueous solution and used.

B. To 162 parts of a 1, 2-Diohloräthanlösung with a content of 55.5 parts of a soluble Chlormethyldiphenylätherpolymerisates with about 23% residual high rare chain chlorine (0.36 mole -CHgCl), 150 parts water and 31 * 8 parts (0.51 moles ) Dimethyl sulfide added. The mixture was heated at 50 to 55 ° C. for 6 hours and then cooled. The cloudy mixture slowly separated into two clear viscous solids. The addition of a further 40 parts of water gave a clear, viscous, light yellow solution of the dimethylsulfonium derivative. The analysis for ionically bound chloride showed that the conversion of the remaining chloromethyl groups was practically complete.

The present invention also encompasses novel soluble functional ingredients Polymers with functional anionic groups, which chemically

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are bound to a (methylenediphenyl ether) polymer. Quite in particular, the invention also relates to soluble derivatives of (Halomethyldiphenylather) polymers, which are characterized by a Variety of (methylenediphenyl ether) residues of the formula

III

denote, in which each radical A is in each case a hydrogen atom or represents a radical -R or -CHgR ,, and R an anionic A radical means that contains a sulfonic acid, carboxylic acid, phosphonic acid or phosphinic acid group and the (methylenediphenyl ether) radicals on average at least 0.05 functional contain anionisohe groups (R).

These new and valuable soluble functional anionic polymers are advantageously produced by chemical modification of a soluble poly (chloromethyldiphenyl ether) direct substitution of a functional anionic group, such as a sulfonic acid or phosphonic acid group on the aromatic nuclei of the polymer. Puncture anionisohe polymers can also be introduced by the introduction of sulfonic acid, amino acid, carboxylic acid, thalolic acid or similar functional anionic residues by reaction

909819/1152

of residual chloromethyl or halomethyl groups of a Wa borrowed (halomethyldiphenyl ether) polymer are produced. These soluble, functional anionic polymers are useful as thickeners, dispersants, flocculants and ohelating agents.

Soluble intermediate product polymers

When carrying out the present invention, a soluble polymer will have a larger molar proportion on a large number of residues of the formula

-0-

in which each radical B individually means a hydrogen atom or a group -CH ₂ Ol or -CHgBr «used as a matrix» to which the anionic groups are chemically bonded. The soluble (methylenediphenyl ether) polymers obtained by controlled condensation polymerization of chloromethyl diphenyl ether and similar reactive diphenyl ether derivatives, as described above, are particularly useful as intermediate polymers.

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- 36 -

As sohon explained, these are essentially linear polymers in methylene chloride, carbon tetrachloride, toluene and soluble in similar non-polar solvents. However, the hydrophobic nature of these soluble intermediate polymerizates becomes changed by the anionic substituents. For example, the addition of about 0.3 or more sulfonic acid groups converts per diphenyl ether the intermediate polymer in a water-soluble derivative, which in water with the formation of a visually homogeneous and transparent solution that can be infinitely diluted with water. The earlier described soluble anionic polymers with at least 0.3 functional groups per diphenyl ether radical are generally in water, soluble in aqueous alcohol, aqueous acetone and similar polar solvents. With a lesser degree of substitution and less hydrophilic substituents, are the solubility characteristics similar to those of the (methylenediphenyl ether) polymers used as intermediate.

Nuclear-substituted anionic derivatives

For the production of an anionic polymer that the contains functional group bonded directly to the aromatic ring, such as a sulfohic acid derivative, such as shown in equation 2 is established

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-O-

-ο-

SO,

(01.2) 1st to the use of a soluble (Methylendiphenylather) -PoIynerisates low remaining halomethyl content as intermediate sohenprodukt practical. In the case of an intermediate polymer with less than 0.1 halomethyl groups per diphenyl ether radical, soluble polymers with up to about 2 anionic substituents per diphenyl ether radical can be produced. It is difficult to obtain a higher degree of direct substitution without undue crosslinking and undue insolubilization.

It is true that the soluble (methylenediphenyl ether) polymer used as an intermediate can be used with common reagents such as concentrated sulfuric acid or chlorosulfonic acid are sulfonated, but extreme care must be taken, keep networking to a minimum. A preferred sulfonation process is the use of a SO, -Phus ~ · phate complex as a sulfonating agent. When using this procedure in the case of a (methylenediphenyl ether) polymer with less as 0, J chloromethyl groups per diphenyl ether residue as intermediate

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U95538

product, this process results in rapid sulfonation with a minimum of crosslinking, which is a soluble anionic Polymer with an average of up to about two sulfonic acid groups per diphenyl ether residue. Sulfenic acid derivatives, the contain more than about 0.2 sulfonic acid groups per diphenyl ether residue, are usually completely soluble in water. There are also salts obtained by neutralizing the sulfonic acid with ammonia, Sodium hydroxide, potassium carbonate, water-soluble organic amines and similar monovalent bases are obtained, in general water soluble.

Derivatives with anionic side chains

Punctiform anionic polymers can also be prepared by introducing sulfonic acid, amino acid, carboxylic acid or thiolic acid residues by reacting residual halomethyl groups of (halomethyldiphenyl ether ) polymers used as an intermediate, as shown in equation 3.

CH ₂ Cl

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BATH ORIGINAL

It is particularly useful for achieving a high anionic content expedient, a (halomethyldiphenyl ether) polymer with a high residual chloromethyl content as an intermediate product, preferably an average of 1.2 to 2.0 chlorinethyl groups per diphenyl ether residue to be used.

Many different soluble anionic derivatives can be prepared in this way by reacting residual halomethyl groups with suitable functional reagents to replace the calogen with a substituent group containing a sulfonic acid or carboxylic acid residue. Suitable functional reagents are characterized Welter by the following features: (l) solubility to the extent of at least 5 wt -% in a polar hydroxyl group-containing solvent such as belspielsweise water, alcohol, ethylene glycol and mixtures thereof, (2) reacting stoichiometric with. Amount of benzyl chloride at 20 to 100 ^° C. with replacement of at least 5 mol # of the chloride content thereof in 48 hours and (5) the presence of a sulfonic acid or carboxylic acid group or a group which can be converted into this by simple hydrolysis. When incorporated into an insoluble resinous matrix, these functional anionic groups yield cation and chelate exchange resins.

Typical of the various functional reagents used to prepare the anionic polymers described here

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can be used by reacting with a halomethyl substituent group «are the following t inorganic salts * such as sodium cyanide, potassium thiocyanide, sodium sulfite; Metal salts of active methylene compounds such as sodium acetic acid and sodium malonitrile; Amino and thio acids such as glycine, iminodiacetic acid, phenylalanine, mercaptosuccinic acid and olycolic acid and salts thereof; Aminonitriles and diethylaminoacetonitrile and the like.

Sometimes the reaction of the soluble Halogenraethyldiphenylätherpolymerisates used as an intermediate with a the desired reagent is complicated by opposite solubility characteristics. The intolerance is particularly bothersome occurs between the intermediate polymer and a hydrophilic reagent such as sodium iminodlaoetate. This difficulty however, it can be circumvented by the general procedure shown in Equation 4, where Ar is a methylene diphenyl ether residue represents.

Me _p S + ''

Ar-CH ₂ Cl - ^d> _Ar-CH2 SMe ₂ Cl ---- j NH (CH ₂ COONa) ₂

-CH ₂ N (CHpCOONa) ₂ (Ql.4)

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This sulfonation process is particularly valuable in the synthesis of soluble methylenediphenyl ether polymers which contain iminodiaoetate or meroaptoacetate groups. Since the sulfonium salts used as intermediates are generally found in water? aqueous alcohol, ethylene glycol and similar solvents containing hydroxyl groups are soluble, these solvents are two-dimensional for the reaction of the salts with the functional reagents. Because of the different nature of the reaction components, however, no solvent or mode of operation is optimal for all systems. A careful choice must be made on the basis of the properties of the reaction components, which can be confirmed by simple experiments.

The following examples illustrate the invention without restricting it. Unless otherwise stated, all parts are and Percentages based on weight.

Example 8

(Ethylene diphenyl ether) polymers as intermediates

A. To a solution of 2650 parts of chloromethyl diphenyl ether with a content of 51 * 5% by weight of chlorine and an average of 2.70 chloromethyl groups per diphenyl ether radical (ClCHg- / DPÄ) and 2650 parts of 1,2-dichloroethane, 16 parts were obtained under PJÜiren added to a 50 # iß9n solution of anhydrous ginkohlorid in methanol

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After heating the Reaktlonsgemisohes at 65 to 70 ⁰ C for 21 hours, anschliessendetn washing with water to remove the catalyst and the dissolved HCl to give 3455 parts of a polymer solution with a Qehalt of 67.2 $ solids. A sample of the soluble poly (ChlormethyIdiphenyläther), which was isolated by precipitation with excess methanol "containing" was found to be 21.7 Qew.- £ side chain chlorine or an average of about 1.60 residual ClCH ₂ groups per DPA.

B. Polymerization of a Chlormethyldiphenyläthers with a content of 17 * 6 parts by weight Jt chloride (1.12 ClCH ₂ -ZDPX) in entepreohender manner gave a soluble (Methylendiphenyläther) -polymerizates for use as an intermediate containing less than 2 wt Ji side chain hollowor or an average of less than

0.1 remaining CICEU groups per DPX contained.

_{C. Various other chloromethyldlphenyl ethers with an average of about 1.0 to 3.0 ClCH 2} groups per DPX can be polymerized to form soluble (methylenediphenyl ether) polymers with an average of about 0.05 to 2.0 remaining ClCH 2 groups per DPX .

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Example 9 Sulfonic acid polymers

A. To a solution of 184 parts (1 mol of DPA content) of the soluble (methylenediphenyl ether) polymer described in Example 8B, dissolved in 3700 parts of 1,2-diochloroethane, cooled in an ice bath with stirring slowly in about 15 minutes a solution of 312 parts (1.7 mol) of triethy! phosphate and 202 parts (2.5 mol) of SO-S was added, the temperature being kept below 10 ° C. during the addition. The ice bath was removed and the The light red solution was stirred for an additional hour while the cloudy mixture slowly warmed to room temperature. Then it was neutralized with an excess of 50% sodium hydroxide and the pale cloudy aqueous product phase separated. Dilution with more water gave a visually homogeneous solution with a Content of about 10 % polymer solids.

A sample of the sulfonated polymer was obtained by dilution part of the aqueous solution precipitated with acetone. The white solid polymer obtained was insoluble in methanol, but easily dissolved again in water. The solid polymer was contaminated with inorganic salts, but it turned out the elemental analysis for carbon, hydrogen, sulfur and Sodium calculated that the polymer contained on average between about 1.5 and 2 sulfonic acid groups per DPA group.

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using standard ion exchange procedures with one strongly acidic resin in hydrogen form, the soluble polymer was converted into the free acid form

B. To determine the usefulness of the sulfonated polymer as a dispersant for titanium dioxide pigment in latex paints « were successive portions of a 6.5-igen -aqueous Solution of the polymer described in Example 2A in the sodium form to give a thick pulpy grinding charge of 300 parts Titanium dioxide pigment and 200 parts of water were added until the batch was converted into a flowable dispersion, which spread smoothly without lumps when poured on a glass plate. In the sulfonated polymer were about 55 parts of the aqueous solution are required to achieve the desired dispersion, i.e. about 1 part of polymer / 100 parts of pigment. In this test, recognized commercially available pigment dispersants are at about 0.3 to 0.7 parts / 100 parts pigment effective.

Example 10 Iminodiaoetatpolymerisat

A. A mixture of 200 parts of the soluble poly (chloromethyl diphenyl ether) described in Example A containing 1.2 mol -CHgCl groups, 500 parts of ethylene glycol diethyl ether and 375 parts of 1,2-dichloroethane was heated to 40 * C, and 96.2

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Parts (1.6 moles) of dimethyl sulfide were added. After 10 minutes of warming to 40 ° C., the reaction mixture was diluted with 1000 parts of water , which were slowly added over a period of 30 minutes . Endlieh the dichloroethane and excess Dinethylsulfid in vacuo at 40 to 50 ⁰ C were stripped.

To 100 parts of the above aqueous solution with a content of about 25 parts of dimethylsulfonium salt (0.11 mol-CH ₂ S ⁴ *) was added a solution of sodium minodiacetate, which was obtained by dissolving 30 parts (0.22 mol) of iminodiacetic acid in about 100 parts Parts of 20 Jiigem sodium hydroxide was made. The resulting black-tan solution was then heated. At about 50 ⁹ C there was a violent development of dimethyl sulphide. After 12 hours of heating at 50 to 70 ⁰ C, the development of Dlmethylsulfid hurte on. To ensure complete conversion, the mixture was then kept at 90 to 95 ° C. for about 10 hours. Dilution with water gave a 5 to 10% aqueous solution of the imodiaoetate polymer which is effective for deactivating copper and nickel ions in an aqueous solution.

By treating part of the polymer solution with dioxane the solid Iminodiaoetatpolymerisat was precipitated from the solution. It is true that the cleaning of the polymer by the simultaneous Precipitation of excess sodium diminodiacetate made difficult, but the infrared spectrum of the isolated foil

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merlsates with the proposed structure Ubereln. The elemental analysis of a polymer fraction caused by reprecipitation Purified from water showed an average of about Hethyleneiminodiacetate group: per diphenyl ether residue.

The present invention also encompasses a method of treating paper by incorporating a. small amount of one Cationic (methylene-phenyl-ether) polymer dispersible in water »the In larger proportions a multitude of Diphenylätherrest contains s, which are bound with Methylenbrüoken are «and have an average of at least 0.05 cationic groups (Z) per diphenyl ether residue. The cationic Groups (Z) are wider than amino / ammonium and / or 8ulfonium groups marked * which are chemically attached to the diphenyl ether residues of the polymer matrix as substituents of the formula

-CH ₂ Z

are bound.

The cationic (methylenediphenyl ether) polymer accordingly contains, as a major part, a large number of residues of the general formula

CH ₂ "

909819/1152

U9553S - 49 -

wherein each radical A is a hydrogen atom or a group -CH ζ * and Z is an amino, ammonium or sulfonium group .

In the treatment of paper with a soluble (Methylendiphenyläther) -polymerizates, as described herein, many advantages "Since the characteristics of the treated paper partially depend on the particular polymer used, the possible cationic substitution allows a considerable adaptability to the To meet the needs of a wide variety of applications. As will be explained in more detail below, the type and number of cationic groups can easily be varied. For example, primary, secondary, tertiary amino groups or quaternary ammonium groups as well as mixtures thereof can be used. In some applications, polymers which contain both ammonium and sulfonium groups are particularly advantageous. The degree of substitution, ie the average number of cationic groups per diphenyl ether radical, can also be varied from just 0.05 to 2 or more.

By suitable treatment with the cationic (methylenediphenyl ether) -Polymer, paper with many improved properties can be obtained. So can improved wet and dry strength without any significant change in the sizing characteristics.

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can be obtained by treatment with sulfonium polymers. In addition, the paper obtained has a softer "handle" than Paper treated with common wet strength resins. The introduction of a small amount of a quaternfiren Ammoniumpolymerisates is very effective to increase Achieve electrical conductivity at low levels of humidity. By using a (methylenediphenyl ether) polymer, the other amino or sulfonium groups in addition to quaternary Contains ammonium groups, not only are the electrical conductivity properties of the paper improved, but the polymer is also more strongly bound to the cellulose fibers, so that at the subsequent treatment of the paper with other aqueous solutions no leaching or bleeding of the electroconductive one Polymerisates takes place. Such impermissible mowing against water is very ambiguous for many other applications as well.

Still other advantages result from the use of cationic (methylenediphenyl ether) polymers. Since the (methylenediphenyl ether) matrix is particularly resistant to thermal and is oxidative attack, these cationic derivatives have good chemical and thermal stability. That with paper coating compounds Quaternary ammonium (methylenediphenyl ether) polymers, which occur frequently, are considerably reduced. Also, for a given level, is more aromatic

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Substitution the cationisohe capacity of the (methylenediphenyl ether) residue is greater than that of the vinylbenzyl polymer. Am Yet another advantage is the ease with which these cationic diphenyl ether polymers are readily accessible and relatively cheap raw materials can. So there are important and essential procedural advantages and great economic advantages in the production of these cationic polymers and their application on paper.

The soluble cationic polymers which are effective according to the invention are preferably carried out by condensation polymerization a halomethyldiphenyl ether with the formation of a soluble (methylenediphenyl ether) polymer produced «the rest Contains halomethyl groups. Duroh reaction of remaining halomethyl groups that are bound to the polymer matrix with suitable organic amines, sulfides, or mixtures thereof are the desired cationic diphenyl ether polymers obtain.

In the practice of the present invention, paper can be used with the cationic (methylenediphenyl ether) polymer can be treated in many ways. Because of its cationic nature, the polymer is strongly attracted to the paper fibers. Therefore, it can effectively cause thinned stock soling

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in the Hollander »in the headbox or at another suitable stage before the formation of the cellulose web. Alternatively, the desired cationic polymer can be brushed onto preformed paper material by coating, «dipping», Calendering or other similar common methods of work for the Impregnation or coating of paper material can be applied. In the production of an electrographic copy paper the electroconductive polymer preferably on the paper base material by immersing the paper in an aqueous solution or Dispersion of the polymer applied. The treated paper is then subjected to calendering, oven drying or other usual way dried.

For convenient handling and measurement, the cationic Dlphenylätherpolymerisat is generally available as an aqueous solution or Dispersion used which contains from about 5 to 30 parts by weight of polymer solids. It is only a small amount of the cationic Polymerisates »generally less than 10% by weight of the dry Paper or paper stock needed »to improve the properties of the treated paper. As little as 0.05 wt. # Of these additives give a noticeable improvement. However, in order to achieve optimum properties, the introduction of 1 to 8% by weight of a solution is generally used in practice (Methylenediphenylether) polymer with an average of at least 0.3 cationic groups per diphenyl ether radical are preferred.

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Because of its cationic nature, the uptake of the polymer * even if it is a dilute slurry of paper stock admittedly quite effective.

It is true that the soluble cationic (methylenediphenyl ether) polymers described here are generally effective for improvement the electrical conductivity of treated paper, as it is for electro graphic reproduction is required, but usually the quaternary ammonium derivatives preferred. Those made from tert-methyl- and dimethylalkylamines are particularly twofold quaternary ammonium derivatives.

The treatment of paper material with the cationic (methylenediphenyl ether) polymers results in the properties of electrical conductivity required for an electrographic copier paper. Paper treated in this way is particularly useful for electrographic printing at a relative humidity of less than 25 %. In practice, the cationic (methylene phenyl ether) polymer is preferably applied to one or both of a preformed paper material as an aqueous solution using conventional procedures. The exact amount applied to achieve the desired electrical conductivity properties can easily be determined by a few simple experiments.

909819/1152

In the electrographic process it is also necessary to have a photoconductive coating on the copy paper. It is often two-fold to apply this photoconductive coating from an aqueous solution after treatment with an electroconductive additive. Since the electroconductive additives described here, particularly the preferred quaternary ammonium derivatives, are water-soluble, they tend to bleed out of the paper material and to migrate into the moist photoconductive layer before it has dried. This results in reduced printability of the paper and poorer reproduction. It is therefore of great importance to further establish that the quaternary electroconductive materials described here, after initial application to the paper, can be made less water-sensitive due to the presence of other and different cationic groups in the polymer structure.

In order to make the applied electroconductive polymer insensitive to water, it is necessary that at least 5 to 10 % and preferably 10 to 20 % or more of the cationic groups of the diphenyl ether polymer are of a type that can react with the treated paper to fix or insolubilize the electroconductive polymer are befehlgt. For example, a particularly effective material is made by reacting a soluble diphenyl ether polymer

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the average of about 1.6 remaining chloromethyl groups each Contains diphenyl ether residue, with 15 NoI-J * bis (2-hydroxyethyl) sulfide "based on the total chloromethyl content of the polymer" and then with enough trimethylamine to remove the remaining, to quaternize unreacted chloromethyl groups »obtained.

In addition to sulfonium groups, quaternary ammonium groups can be used on the basis of hexamethylenetetramine also cause this desired water insensitivity. In addition, the presence of amino groups or amino salts depends on the reaction part of the halomethyl groups of the halomethyldiphenyl ether polymer used as an intermediate with simple aliphatic amines »such as monoethyl or dimethyl amines» also reduces the ease with which the applied polymer is removed from the treated paper. The mechanism for inducing water insensitivity is not clarified but it is evident »that at least with the sulfonium and hexamethylenetetremin derivatives the chemical conversion These derivatives with the cellulose fibers occur when the treated paper is dried.

The usefulness of the soluble cationic ions described earlier. (Methylenediphenylether) polymers as additives for paper and other cellulosic products is not limited to improving the electrical properties of the treated products.

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It has also been found »that these additives also improve other desirable properties * for example the wet and Increase the troublesome strength of the treated products. One with these Paper treated with additives has improved pliability or an improved "handle" compared to conventional polyamide or melamine strength additives.

The following examples explain the invention without restricting it. Unless otherwise stated, all parts and percentages are based on weight.

Example 11 Soluble cationic (methylenediphenyl ether) polymers

A. To a solution of 2630 parts of chloromethyldlphenyl ether with a content of 31.5 wt .- ^ chlorine and an average of 2.70 chloromethyl groups per diphenyl ether residue (ClCHgVDPX) and 2630 parts of 1,2-dichloroethane were stirred with 16 parts of a 50-liter Solution of anhydrous zinc chloride in methanol added. The polymerization to a soluble diphenyl ether polymer was achieved by heating the resulting mixture at 65 to 70 ° C. for 21 hours. After washing with water to remove the catalyst and dissolved HCl, 3 ^ 53 parts of a polymer solution with a solids content of 67.2% were obtained. A sample of the polymer, which by precipitation with excess

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gem methanol was Isolated "showed a content of 21.7 wt £ Seltenkettenohlor or borrowed average about 1.60 ClCH ₂ groups per DPX.

B. To 200 parts of this polymer solution containing 154.5 parts of the soluble chloromethyldiphenyl ether polymer, 195 parts of water containing 2.5 parts of sodium hydroxide and then 386 parts of 25% aqueous trimethylamine were added with stirring. The reaction temperature rose to about 45 ° C. After a further 2 hours at 40 to 45 ^° C., the amination was complete, as the analysis of ionically bound chloride showed. The aqueous phase of the product was separated off and concentrated to remove traces to remove 1,2-diehlorethane and excess triethylamine. The remaining clear aqueous solution contained 41.6 % by weight of a soluble quaternary trimethylammonium derivative of poly (methylenediphenyl ether). This cationic 'niche product had 20 #ige aqueous solution has a Brookfield viscosity of 17 oP at 24 ^e C (75 ^e P) and a pH of 7 # 0th

C. In corresponding catfish as described above under Section A, different chloromethyl diphenyl ethers with an average of about 1.0 to 3.5 chloromethyl groups per molecule with the formation of polymerized soluble polymers with an average of about 0.05 to 2.5 residual chloromethyl groups per diphenyl ether radical. Bromomethyldiphenyl ethers polymerize accordingly.

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In the preparation of cationic derivatives of the soluble halomethyldiphenyl ether polymers by the general processes described above under B, a temperature of 20 to 45 ° C. is usually preferred for the amination, while a temperature in the range of 30 to 70 ° C. is often preferred for the reaction of the remaining halomethyl groups is two-dimensional with organic sulphides. In the preparation of the mixed cationic polymers, an amount of the less reactive reagent *, calculated on the basis of the content of residual halomethyl groups and the desired degree of substitution, is usually added first and allowed to react to the desired degree. Then a sufficient amount of the more reactive reagent is added * to convert the remaining halomethyl groups into cationic groups.

Typical examples of the soluble cationic Diphenylätherpoty merisate prepared by this general procedure are given in Tables VI and VII. Except for the dimethyldodeoylamine derivative which gave a cloudy dispersion in water but was completely soluble in aqueous methanol, these cationic derivatives were all at least 1 % soluble in water at room temperature.

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Example 12 Electrical Conductivity Tests

As a preliminary hatred of the effectiveness of the various kationisohen Diphenyl ether polymers for improving the electrical conductivity of paper, the surface resistance of treated test sheets was determined according to the method described in ASIH D-257-61 certainly. Although this test is sensitive to minor changes in the procedure »but those were concurrent Tests obtained values are generally reproducible within a factor of 10.

The test procedure involved coating a standard weighted test sheet of 23 * 2 kg per ream (51 lbs./ream) of bleached sulfite paper "which was sized on one side with the desired cationic polymer" which was generally 25 pounds aqueous solution using a conventional wire-wound Heyer rod applicator to achieve about a 7 to 8-pound strength Polymer uptake, based on dry weight «was applied. The treated sheets were placed in an oven at 110 ° C for 5 minutes (250 * P) dried * weighed and cut into test strips. The ' Test strips were then placed on the surface for 24 hours at room temperature (about 23 ° C) before measuring the surface conductivity desired test humidity conditioned.

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Typical values for the surface forest level of paper «that with various soluble * as described in Example 11 «prepared cationic Dlphenylätherpolymerlsaten treated war «are given in Tables YI and VII. The used Katlonisohen polymers are in the tables by the remaining chloromethyl content of the used as an intermediate Polymerisates “printed out as a rare chain hollowor” by the one used in the preparation of the cationic derivative Amine and / or sulfide and by the average number of cationic groups (Z) per diphenyl ether radical (average Z / DPÄ). This latter ratio was derived from the halomethyl content of the intermediate polymer and the molar ratio of the amine and / or sulfide reaction components calculated.

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Table VI Electrical conductivity of paper coated with soluble cationic methylenediphegyl

ätherpolymerisa th was treated

Cationic Methylendiphenyläther p olymerisat

Surface resistance

Mr. Sew .- #
Cl ^a Amine and / or
sulfide average
Z / DPÄ ² 1-1 8.8 Trimethylamine 0.50 1-2 21.8 Trimethylamine 1.60 1-3 21.8 Dimethylamino
ethanol 1.60 1-4 21.8 Tr i -n-propylamine 1.60 1-5 23.3 Tr i -n-butylamine 1.75 1-6 23.3 N, N-dimethylaniline 1.75 1-7 21.0 Dimethyldodecyl
amine 1.50 1-8 21.0 Pyridine 1.50 1-9 26.9 Thiodiglycol 2.20

Uh-treated control test sheets

Polymer absorption

7.0 % 7.8 % 7.4 #

9.3 * 12.4 %

5.4 %

7.2 %

6.3 # 6.3 *

7% rel.F. 33 % rel.F. 57 »5 4> rel.P.

4.8 χ 10 ¹⁰ 7.6 10 ⁸ 5.0 χ 10 ⁷

3.0 χ 10 ⁹ 2.3 x 10 ⁸ 1.4 χ 10 ⁷

4.5 Χ * 10 ¹¹ 4.2 χ 10 ⁹ 1.0 χ 10 ⁸

1.4

1.0

1.4

4.2

1.7 1.2

χ 10 ¹² 4.1 χ 1O ⁹ 6.0 χ 10 ⁷

χ 10 ¹⁵ 6.0 χ 10 ¹⁰ 4.5 x 10 ⁸

χ 10 ¹¹ 5.4 χ 10 ⁹ 2.7 x 10 ⁸

χ 10 ¹² 4.2 χ 10 ⁹ 1.1 χ ΙΟ ⁸

x 10 * 9.0 x 10 ⁸ 5.3 x 10 ⁷

χ 10 ¹² 1.0 χ 10 ¹⁰ 1.9 χ 10 ⁸

χ 10 ¹⁵ ) c > (8 χ 10 ¹³ ) c 1.2 χ 10 ¹¹

a. Weight Ji side chain chlorine in the chloromethyldiphenyl ether polymer used as an intermediate.

b. Average number of cationic groups per diphenyl ether residue.

c. Drösser as a maximum instrument reading of 8 χ 10 - ^

cn cn co

Table VII

Electrical conductivity of paper that is mixed with soluble cations Methylenediphenyl & therpolymerlsaten was treated

Cationic methylenediphenyl ether polymer surface resistance, Λ

No. Oew.-jß amine and / or average 1st polymer 7 % 33 % 57.5 % to Cl ^a sulfide Z / DPK & uptake rel.P. rel.P. rel.P.

CO 2-1 24.8 Trimethylamine +
Dimethylamine 0.95
0.95 CO
CO 2-2 24.8 Trimethylamine +
Monomethylamine 1.24
0.66 2-3 18.1 Trimethylamine +
Thiodiglycol 0.75
0.50 cn
IO 2-4 21.3 Trimethylamine +
Hexamethylenetetramine 1.04
0.51 2-5 21.8
Untreated Hexamethylenetetramine
+ Thiodiglycol
> Inspection office 1.23
0.37

6.4 "Ji 3.6 X 10 ⁹ 2.4 χ 10 ⁸ 2.9 x 10 ⁷

7.2 % 7.4 x 10 ⁹ 3.0 χ 10 ⁸ 4.3 x 10 ⁷ 13.5 % lA * 10 ¹⁰ 2.7 x 10 ⁸ 5.6 X 10 ⁶

8.3 % 3.4 χ 10 ¹⁰ 8.4 χ 10 ⁸ 6.0 χ ΙΟ ⁷ 9.6 % 1.4 χ 10 ¹² 9.0 χ 10 ⁹ 2.3 x 10 ⁸

»(8 χ 10 ¹⁵ ) c> (8 x 10 ¹³ ) o 1.2 χ 10 ¹¹

a. Weight -56 rare-chain chlorine in the chloromethyldiphenyl ether polymer used as an intermediate. jst

b. Average number of cationic groups per phenyl ether residue. cx>

c. Larger than the maximum instrument reading of 8 χ 10 ^ Jt. · ^,

It can be seen from the values in Tables VI and VII that treatment with these soluble cationic (methylenediphenyl ether) polymers is effective in reducing the surface resistance of paper, ie increasing its electrical conductivity. The degree of effectiveness is influenced by factors such as the cationic content of the polymer, the amount of polymer introduced into the paper (polymer uptake) and the structure of the cationic groups. Under the test conditions given in these tables, the additives set the surface resistance by a factor of ICr to 10 at 57 * 5 % relative humidity, at least. 10 ^ to 10 ⁵ at 33 % rel. P. and more than 10 ¹ to 10 * at 7 % rel. down.

Example 13 Blektrofax test sheet

Using a 20% aqueous solution of the electroconductive test polymer and a standardized wire-wound Heyer rod applicator, test sheets of 18.2 kg (40 lb) of paper material, which had been prepared for use in the electrofax process, were about 0.4.5 to 0 on one side , 68 kg (1.0 to 1.5 lbs) of electroconductive polymer / 307 m ² x (3300 ft ² ) paper surface or about 2.5 to 4.0 weight percent of the charged polymer on a trooken weight basis. The back of each bow was then similar to a catfish

909819/1152

H.95538

photoconductive layer of zinc oxide in a styrene-butadiene latex binder forming a uniform topcoat of approximately 10 kg / 507 m (22 lbs / 3300 f t) on a dry weight basis coated. After aging these test sheets for about 24 hours at the desired humidity level, prints were made according to the electrographic method using a standard test sample and a commercially available liquid toner manufactured. The quality of each print was determined by careful comparison with control prints. Typical results are given in Table VIII.

909819/1152

Table VIII

co ο co

Electrofax test sheet

Test results

5Jr *

Katioriisciies BPÄ polymer

Amines

Surface resistance Λ. Copy intensity

Return

no

1-2 trimethylamine

1-3 rel.P. 56 % RH 25 # rel.P. 65 % RH

bleed out

2-1 2-4

2.0 χ 10 ^U 4.4 χ 1.5 x 10 ⁹ 1.6 χ bad
very good

Well
very good

Dimethylaminoethanol

Trimethylamine + dimethylamine

5.2 χ ΙΟ ¹⁰ 5.3

excellent- very good

net

1.7 x 10 ⁸ 1.2 χ 10 *

Trimethylamine

+ Hexamethylene _Q

tetramin 5.8 χ ΙΟ- '8.4 χ 10 very good very good

intense none none weak none considerable

very good very good none

no

none

none

a. At 25 % RH

cn cn GO

The typical test results given in Table VIII « show that by treating the paper material with the cationic ions (Ethylene diphenyl ether) polymers improved electrographic Copy. It should be noted that the copy back caused by insufficient electrical conductivity Treatment with the cationic polymers was eliminated. The bleeding of the electroconductive polymer in the photoconductive Layer «as it looks through blotchy or speckled The appearance of the printed sheet was particularly conspicuous with the dimethylaminoethanol derivative. However, as shown in Table VIII and emerged from other similar tests, makes presence of smaller amounts of non-quaternary cationic groups in the soluble diphenyl ether polymer, the electroconductive one Polymer is immobile and therefore gives a more uniform Print quality.

BATH OFUGINAL

909819/1152

Claims (1)

Claims 1. Dissolvable diphenyl ether polymer, characterized by a major part of a large number of radicals of the general formula -0- wherein each radical A, independently of one another, ^{denotes a hydrogen atom, a radical R 9} or a group -CHgY or -CH ₂ R "where Y is a chlorine or bromine atom or an OH-Q group or OR group and R is an alkyl group with 1 represents up to 4 carbon atoms and R ^{4 contains} as functional group a group -SO Ji or -COOfI or -POJl ₂ and -HgPOgM, in which H is a monovalent cation. 2. Soluble diphenyl ether polymer according to claim 1, characterized marked * that there are at least 0.05 halomethyl groups each Contains Dlphenylätherrrest. j $. Soluble Diphenylätherpolymerisat according to claim 1 "characterized in that there are about 1.0 to 30.0 wt -% contains in the side chain is bound chloride.. 909819/1152 4. Soluble polymer according to claim 1, characterized in that R ^{1 represents} a sulfonic acid group or monovalent cationic salts thereof. 5. Water-soluble, functional anionic polymer, characterized »that it essentially consists of a large number of (methylene diphenyl ether) radicals» which contain an average of at least 0.3 anionic groups per (methylene diphenyl ether) radical bonded chemically to their aromatic nuclei »where the anionisohen O-groups are -SO-M, -VQJH ^ or -HPO ₂ M, where H is a monovalent xatlon. 6. Water-soluble anionic polymer naoh claim 5, characterized characterized in that there are on average about 0.3 to 2.0 sulfonic acid groups per (methylene diphenyl ether) radical and / or monovalent contains cationic salts thereof. 7. Water-soluble functional anionic polymer, characterized in that it consists essentially of a large number of (methylenediphenyl ether) radicals which are chemically bonded to their aromatic nuclei on average at least 0.3 substituents of the formula -CH ₂ R per (ethylenediphenyl ether) radical where R is an halogenic radical which contains a group SOJi or -COOK, in which H is a monovalent cation, as a functional group. 909819/1152 Ή95538 8. Water-soluble anionic polymer according to claim 7, characterized in that it averages about 0.3 to Methyleniminodiaoetatgruppen Je (methylenediphenylether) radical as Contains substituents. 9 · Water-soluble anionic polymer according to claim 7 / characterized in that there is an average of about 0.3 to methylene mercaptosucoinate groups * j e (methylenediphenyl ether) radical contains as substituents. 10. Water-soluble anionic polymer according to Anspruoh 7, characterized in that there is an average of about 0.3 to 2 methylene sulfonic acid groups per (methylenediphenyl ether) residue as Contains substituents. 11. Water-soluble anionic polymer according to claims 7 »characterized in that it is on average about 0.3 to 2 methylenecarboxylic acid groups per (methylenediphenyl ether) residue contains as substituents. 12. Process for the production of a soluble diphenyl ether polymer, which contains a large number of diphenyl ether groups bonded with methylene bridges, characterized in that a reactive aromatic material, which 1. has a main 909819/1152 H95538 - 70 part by weight of a diphenyl ether of the general formula wherein each radical A independently represents a hydrogen atom or a group -CHgY * wherein Y represents a chlorine or bromine atom or an OH group or an OR group and R represents an alkyl group with 1-4 carbon atoms and 2. average borrowed in approximately 1.0 - 3 »5 -CRgY groups per molecule is subjected to condensation polymerization, wherein the polymerization in the presence of an inert diluent and a Friedel-Crafts · catalyst at a temperature in the range 0-85 ^Ä C. 13. The method according to claim 12, characterized in that a halomethyl diphenyl ether as the reactive aromatic material is used with an average content of about 1.0 to 3.5 halomethyl groups per molecule. 14. The method according to claim 12, characterized in that a halogenated aliphatic hydrocarbon is used as the diluent. 15. The method according to Anspruoh 12, characterized in that as Catalyst stannous chloride is used. 909819/1152 U95538- - 7i - 16. The method according to claim 12 »characterized in» that zinc chloride is used as a catalyst. 17. Process for the preparation of a soluble diphenyl ether homopolymer, characterized in that » a.) a mixture of 10 parts of a chloromethyldiphenyl ether with an average content of about 1.0 to 3.5 chloromethyl groups per molecule of diphenyl ether »10 to 90 parts of a halogenated aliphatic hydrocarbon and 0.01 to 0» 1 part of anhydrous stannous chloride at one temperature between 0 and 85 ⁰ C for a sufficient time to achieve a soluble diphenyl ether homopolymer is implemented and b.) the polymerization before the Qelbildung by adding Water is canceled to inactivate the catalyst. 18. Soluble cationic polymer »characterized» that there is a large number of diphenylsther residues as the main part » linked to methylene bonds and cationic groups (Z) ohemisoh to the aromatic nuclei of the diphenyl ether radicals as substituents of the formula -CH ₂ Z contains bound »contains. 909819/1152 H95538 19 · Soluble catalytic polymer according to claim 18, characterized marked "that the cationic groups (Z) ammonium-" Are sulfonium and / or phosphonium groups. 20. Soluble cationic polymer naoh claim 18, characterized characterized «that it contains an average of at least 0.05 functional groups (Z) per diphenyl ether residue. 21. Soluble, cationic polymer «characterized« that it essentially consists of a large number of diphenyl ether residues, which are connected with ethylene broths and have an average of at least 0.05 cationic groups (Z) per diphenyl ether residue, where the cationic groups ohemisoh to the aromatic nuclei of the diphenyl ether radicals as substituents of the formula -CH ₂ Z are bound. 22. Water-soluble cationic polymer, characterized in that “it consists essentially of a large number of diphenyl ether residues,” which are associated with Nethylenbruoken and contain an average of at least 0.3 cationic groups (Z) per diphenyl ether residue, the cationic groups ohemisoh to the aromatic nuclei of the diphenyl ether groups 909819/1152 all substituents of the formula -CW ₂ Z are bound. 23. Water-soluble cationic polymer according to claim 22 « characterized in that the cationic groups (Z) are ammonium, sulfonium and / or phosphonium groups. 24. Cellulose-containing product «daduroh marked« that Cellulose fibers at least 0.05 ow.-Ji, based on trookenen Paper stock «on a soluble cationic (methylene phenyl ether) polymer with an average of at least 0.05 cationic groups per diphenyl ether residue, the cationic groups being attached to the aromatic nuclei of the polymer are bound by a methylene group. 25. Product naoh claim 24 «daduroh characterized that the cationic groups are amino, ammonium, quaternary ammonium or sulfonium groups, or hemisoles thereof. 26. Process for the production of electroconductive paper " daduroh characterized «that an aqueous solution of a water-soluble kationisohen (Methylendlphenyläther) polymer the average of at least 0.3 quaternary ammonium groups 909819/1152 H95538 each contains diphenylate residue, applied to a paper material in this way * that in this about 0.05 means 10.0 wt .- #, based on trookenen Paper stock * to be added to polymer «and then trooknet the paper. 27 «Process for the production of paper with improved wet and dry strength, characterized in that one Paper material suspension about 0.05 to 10 * 0 Qew.- £, based on trookenen paper stock »of a soluble cationic (methylene-phenyl ether) polymer, whereby the kationlsohe polymer contains an average of at least 0.3 sulfoniura groups per diphenyl ether residue, and then one Paper web forms and this trooknet. 90981 9/1152